Substituent effects on H3+ formation via H2 roaming mechanisms from organic molecules under strong-field photodissociation

Ekanayake, Nagitha; Nairat, Muath; Weingartz, Nicholas P.; Michie, Matthew J.; Levine, Benjamin G.; Dantus, Marcos

doi:10.1063/1.5065387

Substituent effects on H₃⁺ formation via H₂ roaming mechanisms from organic molecules under strong-field photodissociation

Journal Article · Mon Dec 31 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5065387· OSTI ID:1610693

^[1]; Nairat, Muath ^[2]; Weingartz, Nicholas P. ^[2]; ^[2]; ^[2]; ^[2]

Michigan State Univ., East Lansing, MI (United States); DOE/OSTI
Michigan State Univ., East Lansing, MI (United States)

Roaming chemical reactions are often associated with neutral molecules. The recent findings of roaming processes in ionic species, in particular, ones that lead to the formation of H³⁺ under strong-field laser excitation, are of considerable interest. Given that such gas-phase reactions are initiated by double ionization and subsequently facilitated through deprotonation, in this work we investigate the strong-field photodissociation of ethanethiol, also known as ethyl mercaptan, and compare it to results from ethanol. Contrary to expectations, the H³⁺ yield was found to be an order of magnitude lower for ethanethiol at certain laser field intensities, despite its lower ionization energy and higher acidity compared to ethanol. In-depth analysis of the femtosecond time-resolved experimental findings, supported by ab initio quantum mechanical calculations, provides key information regarding the roaming mechanisms related to H³⁺ formation. Results of this study on the dynamics of dissociative half-collisions involving H³⁺, a vital cation which acts as a Brønsted–Lowry acid protonating interstellar organic compounds, may also provide valuable information regarding the formation mechanisms and observed natural abundances of complex organic molecules in interstellar media and planetary atmospheres.

View Accepted Manuscript (DOE)

Research Organization:: Michigan State Univ., East Lansing, MI (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0002325

OSTI ID:: 1610693

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 149; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited By (4)

Collision-induced and complex-mediated roaming dynamics in the H + C ₂ H ₄ → H ₂ + C ₂ H ₃ reaction Fu, Yan-Lin; Lu, Xiaoxiao; Han, Yong-Chang Chemical Science, Vol. 11, Issue 8 https://doi.org/10.1039/c9sc05951b	journal	January 2020
Quantum coherent control of H ₃ ⁺ formation in strong fields Michie, Matthew J.; Ekanayake, Nagitha; Weingartz, Nicholas P. The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5070067	journal	January 2019
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